Solubilization of metallic-8-quinolinolates



United States Patent SOLUBILIZATION 0F METALLIC-8- QUINOLINOLATES Robert Feigin and Morris P. Schwartz, Providence, R. L,

assignors to Geigy Chemical Corporation, a corporation of Delaware No Drawing. Application February 29, 1952, Serial No. 274,312

14 Claims. (Cl. 260-270) This invention relates to the solubilization of metallic- 8-quinolinolates to form concentrates thereof, which are soluble in liquid organic solvents, especially in Stoddard solvent, mineral spirits or other commonly employed volatile organic solvents of relatively low cost. It relates more particularly to the solubilization of copper-8-quinolinolate,

.to form a concentrate thereof which is capable of dilution insoluble, but nevertheless important of these. It has the following structural formula:

H H H H at at. HC CO Cu--OC CH I HCi 1 N; ;CH C C C-C 1'1 1'1 1'; it

Copper-8-quinolinolate Copper-S-quinolinolate is known and recognized as one of the most effective fungicidal compounds. It is of great value therefore as a preservative and mildew-proofing agent for cotton, wool, synthetic fibers of all types, wood, concrete and plastics. Because of its insolubility, its application to such materials has been largely restricted to coarse dispersions in both water and non-aqueous solvents. Under such conditions the applications are often non-uniform, non-penetrating, and susceptible of leaching after application.

It has been proposed to react a water-insoluble heavy This invention also relates to the concentrate per 'se 2,755,280 Patented July 17, 1956 ice 4C1 olate because of its use as a fungicidal composition. It has been shown by Vicklund and Manowitz in CADO, Technical Data Digest, vol. 15, issue No. 5, year 1950,

pp. 18-21, that the fungicidal activity of this last com-.

pound is reduced by the presence of other metals.

Another object is that solubilizers are employed in securing the concentrated solution of the metallic-8-quinolinolate which are either colorless or very light colored generally. The solubilizers are or can be selected moreover which are aromatic or fully saturated aliphatic compounds which are stable, non-oxidizing and non-yellowing in their properties. They also enhance the substantivity of copper-8-quinolinolate for fibrous materials and surfaces.

A still further object of this invention is to prepare concentrated solutions of any of the aforesaid metallic-8- quinolinolates which are capable of dilution in a large number and many different kinds of liquid organic solvents; and the resulting dilute solutions, more particularly of the copper derivative possess particular effectiveness as ,3 fungicidal and fungistatic sprays and impregnants.

metal soap, especially a zinc soap, nickel soap or aluminum (U. S. Patents Nos. 2,561,379 and where the heavy metal soaps or aluminum soap are used.

Another object is to form a concentrated solution of the aforesaid S-quinolinolate without the introduction of any other metal than in this compound itself. This is of more important consideration in the case of copper-8-quinolin These and other objects will become apparent from reading the following description of the invention:

According to this invention, it has been found that copper-8-quinolinolate can be dissolved to form a concentrated solutionjin an acid ester of certain diand tricarboxylic acids and certain alcohols which ester is polar in nature. Furthermore, the solubilizingaction is enhanced if there is present an aromatic nucleus, or a free alcoholic hydroxyl group in the alpha or beta position to the carboxyl group, or preferabiy both an aromatic nucleus and a free alcoholic hydroxyl group, in the chemical structure of, the solubilizer. The ester linkage COOR- confers polarity, yet these two aforesaid designated groups increase the polarity which is correlated to the greater solubilizing potentiality for copper-8-quinolinolate in the concentrated solution. The preferred solubilizers are liquid materials but solid and semi-solid substances are also effective, although more difficult to handle. Whereas there has been specifically mentioned copper-S-quinolinolate supra, which is more important because it is a particularly effective fungicide, we have been able to dissolve and form the concentrate of other water-insoluble metallic complexes of 8-hydroxyquinoline. These metallic compounds include nickel, cobalt, lead, zinc, iron, aluminum, magnesium, manganese and tin. This embraces the metallic classifications known as the iron group, tin group, themagnesium group, the aluminum group and manganese, as well as the preferred copper. We have designated the resulting products from dissolving the metallic- S-quinolinolates in the polar acid esters, which solutions are usually liquids, as concentrated solutions; this term will be employed throughout.

The acid esters of organic diand tri-carboxylic acids are in general preferred to sulfuric, sulfonic, sulfinic, phosphoric, phosphinic and other inorganic acids, since the latter are injurious to textile fabrics and other types of organic matter.

The acid radical of the hydrogen or acid esters which are the solubilizers of the present invention is of the dior tri-carboxylic acid types. A partial list is maleic,

Y succinic, aconitic, itaconic, tricarballylic, dilinoleic, sebacic, adipic, diglycollic, citric, tartaric, phthalic, and methylene disalicylic acids. These come under the classification of: (l) paraffin di-carboxylic acids, from which above list are to be found succinic acid, adipic acid and sebacic acid, (2) hydroXy-paraflin di-carboxylic acids, from which above list is to be found tartaric acid, (3) olefine di-carboxylic acids, from which above list are to be found maleic acid, itaconic acid and dilinoleic acid, (4) olefine tri-carboxylic acids, from which above list is to be found aconitic acid, paraffin tri-carboxylic acids from which above list is to be found tri-carballylic acid, (6) hydroxy-paraffin tri-carboxylic acids, from which above list is to be found citric acid, and (7) phenyl di-carboxylic acids, from which above list is to be found phthalic acid. Anhydrides of the di-carboxylic acids in the above disclosure, under the conditions of reaction to be described, give products which are identical with those obtained by the utilization of the acids themselves.

The alcohol radical of the hydrogen or acid esters which are the solubilizers of the present invention can be of various types as to be seen from the list set out below. The alcohol radical can be that of a fatty alcohol, such as n-decanol, oleyl alcohol, and stearyl alcohol, which correspond to the higher fatty acids present as glycerides in fatty oils and fats, as well as glycols, and certain cyclic alcohols such as ethyl hexanol, trimethyl nonyl alcohol, dipropylene glycol, tripropylene glycol, polyoxyethylene glycol, ethylene glycol butyl ether, dipropylene glycol methyl ether, diethylene glycol butyl ether, ethylene glycol p-sec.-butyl phenyl ether, ethylene glycol p-tert.-butyl phenyl ether, propylene glycol monophenyl ether, ethylene glycol phenyl ether, trimethyl cyclohexanol, benzyl alcohol, hydroabietyl alcohol, p-octyl phenoxyethanol, and 6,6-di-methylbicyclo-(1,1,3 )hept.-2ene-ethanol.

There are various types of acid or hydrogen esters of organic polycarboxylic acids and an alcohol, polar in their nature, which will dissolve copper-S-quinolinolate and other water-insoluble metallic complexes of 8-hy' droxyquinoline. They are discussed in their order of preference.

One type is the polar, acid ester containing one or more aromatic nuclei and also one or more alcoholic hydroxy] groups in the alpha or beta position to the carboxyl group. This type generally possesses powerful solvent action for copper-8-quinolinolate and for other metallic derivatives thereof, such as those of Ni and Zn. This is consequently the preferred type of solubilizer. An illustrative example of this is the acid ester formed from 2.0 mols. of ethylene glycol p-sec. butylphenyl ether and 1.0 mol. of citric acid.

The second type is the polar, acid, ester containing one or more aromatic nuclei, but no free alcoholichydroxyl group. The aromatic nucleus may be in the carboxylic acid portion, but it may also be in the alcohol portion. of the compound. An illustrative example is the partial ester formed from 1.0 mol. of dipropylene glycol and 1.0 mol. of phthalic anhydride. An illustrative example wherein the alcohol radical appears in the alicyclic type, is the partial ester formed from 1.1 mols. of 6,6.-dimethylbicyclo-(1,1,3)-hept.-2-ene-ethanol and 1.0 mol. of phthalic anhydride. Still another illustrative example is the partial ester formed from 1.1 mols. of propylene glycol monophenyl ether and 1.0 mol. of phthalic anhydride. When the esterifying acid is maleic, succinic, adipic, aconitic, itaconic, tri-carballylic, dilinoleic, sebacic or diglycollic acid, then the aromatic nucleus is only in the alcohol radical portion of the compound. These are acid esters of parafiinic di-carboxylic and tri-carboxylic acids and aliphatic olefine dicarboxcylic acids, the olefinic linkages also contributing to polarity as mentioned supra.

A third type, which has no aromatic nucleus but does contain a free alpha or beta hydroxyl group, is the acidic partial ester of an alpha or beta hydroxy aliphatic acid and an aliphatic or alicyclic alcohol. An illustrative example of this is the partial ester formed from 1.0 mol. of citric acid and 2.0 mols. of 3.35 trimethyl cyclohexanol. Its polarity is due to the ester linkage, the alcoholic hvdroxyl group and the free carboxylic group.

The fourth type, which has no aromatic nucleus or fre hydroxyl group, is the acid or hydrogen ester of an ole-. fine dicarboxylic acid. An illustrative example of this is the acid ester formed from 1.0 mol. of maleic anhydride CHCO and 1.2 mols. of N-decanol. Here the polarity is obtained by the ester linkage, the unsaturated C=C linkage and the free carboxylic group.

In general, the preferred equivalent weight of the hydrogen or acid ester solubilizers of our invention should be within the range of 100 to 750, equivalent to acid values between and 560 milligrams of KOH per gram. The optimum equivalent weight of the solubilizer is 350-500.

' As has been already pointed out in the disclosure supra, the solubilizers of the present invention are acidic organic media which are polar in nature. Benzyl alcohol, a neutral material, is a powerful solubilizer for copper-S-quinolinolate, but it is ineffective on dilution in liquid hydrocarbon solvents. However, when esterified with a di carboxylic or tri-carboxylic acids, the resultant acid ester is an unusually powerful solvent for this compound upon dilution in aromatic solvents. This behavior or property is very important in the usage of this copper compound which is particularly effective as a fungicide and as a mildew-proofin g agent.

- Whereas we have given various types of acid or hydrogen esters of diand tri-carboxylic acids and alcohols, polar in nature because of their chemical structure, the choice of the solubilizer in respect to the diluent, especially for low concentrations, must be considered. It is elemental that in order to. obtain a concentrate of the quinolinolate that is dilutable in some selected solvent, such as, mineral spirits or Stoddard solvent, the solubilizer should be selected or synthesized so that the solubiliur itself is soluble in the particular diluent. Since a low concentration, usually 1% for copper-8-quinolinolate, is applied in practice, the concentrated copper-S-quinolinolate solution, must of necessity, be capable of dilution in common volatile organic solvents, such as mineral spirits, Stoddard solvent, xylol, pine oil, turpentine, chlorinated solvents such as carbon tetrachloride, perchlorethylene and o-di-chlorobenzene, ethyl acetate, butyl acetate, lacquer thinners and other low cost volatile solvents. For uses other than for fungicidal sprays or impregnants the matter of volatility of the liquid, organic diluent is secondary.

It is desirable to have concentrated solutions that are readily soluble on dilution at, or slightly above, room temperature. We have found that the concentrated solutions of copper-S-quinolinolate which we have prepared by the numerous examples herein, are even more soluble at room temperature than at elevated temperatures. This is an inverse solubility relationship to the normal in reference to temperature. The preferred method of dilution is to slowly add the diluent to the concentrates of the metallic quinolinolates to first thin them out. The major portion of the solvent can then be incorporated with little or no further agitation.

There are several precautions which should be taken for securing satisfactory concentrates in accordance with this invention. It is desired to avoid either reduction of the copper compound to copper, or the oxidation of organic matter. To this end it is desirable to use an atmosph ere of carbon dioxide, nitrogen or other inert gas toprevent the oxidation of organic matter which is accompartied by reduction of the copper in the chemically bound condition to the metallic state. Chemical anti-oxidants may also be incorporated if desired.

'In view of the fact that copper in the compound is easily reduced and the 8-hydroxyquinoline is oxidized, it is desirable to avoid the use of any oxidizing or reducing ingr edients in the composition, either the concentarted solution or the diluted solutions, commercially usable particularly as sprays or impregnants. The polar, acid or hydrogen esters of diand tri-carboxylic acids appearing in the examples herein do not contain either oxidizing or reducing groups which would oxidize 8-hydroxyquinoline or reduce copper or other polyvalent metals present. Whereas the time of preparation of the concentrate solution in the laboratory is often of short duration, in actual commercial production because the batches are large, times of heating are necessarily longer; and therefore chemical oxidants and reductants have a. greater effect.

It is not necessary to employ pure chemical compounds or compositions to solubilize copper-S-quinolinolate or other metallic complexes of 8-hydroxyquinoline. It is possible to employ incompletely reacted acid esters as shown in many of the examples forming part of this disclosure. Mixtures of various types such as mixed ester products having two or more alcohol radicals or acid radicals may also be used. The solubilizers may be synthetically prepared while dissolving copper-S-quinolinolate in situ. Another alternative is to simultaneously prepare the copper-S-quinolinolate in situ from a basic copper salt and 8-hydroxyquinoline while forming the acidic ester from an organic di-carboxylic or tri-carboxylic acid and an alcohol, giving the concentrated solutions. Although in making reference to various alternative methods the reference has been to copper-8-quinolinolate, the assertions are applicable to other metallic quinolinolates as well.

In the preceding paragraph there has been repeated mention made of the solubilizers, the acid esters of diand tri-carboxylic acids. The techniques employed in esterification are very well known and varied. Insofar as the esterification per se and as an unit process as such is concerned we are generally employing conventional or known methods. We recognize that the use of a catalyst, an azeotropic fluid, reduced pressure or special mechanical equipment to facilitate or promote an esterification has been utilized both in laboratory and plant operation. But there should be avoided the use of those chemicals and conditions that chemically alter the components. As has been pointed out supra, copper in the copper-8-quinolinolate is easily reduced to the metallic state and 8-hydroxyquinoline just as easily oxidized. The polar, acid ester can be prepared with a very powerful catalyst and/ or under reduced pressure, wherein the reaction temperature is too low at that stage to dissolve copper-8-quinolinolate; but it can be brought into solution at'another or subsequent stage, thus coming within this invention.

The following examples set forth specific embodiments of the invention but are not to be construed as limiting the same. The first examples pertain to solubilizing cop- -per-8-quinolinolate, while the last two examples relate to solubilizing the zinc and the nickel derivative thereof respectively.

These numerous ester preparations have been found to dissolve the specified copper, nickel and zinc-8'-quinolinolates as set out. It will be observed that citric acid and phthalic anhydride have been used in the synthesis of most of the solubilizers. These esterifying compounds are desirable, since their partial ester derivatives are generally non-crystallizing, viscous liquids. In the examples where the term parts appears, this refers to parts by weight. In the disclosure above the polar, acidic partial esters solubilizers have been designated by four types. This arrangement will be adhered to below, and in the preferred order by type.

TYPE I Example 1 ble on dilution at room temperature in Stoddard solvent, xylol, pine oil and turpentine. The material is a viscous liquid which does not crystallize on storage at low temperatures.

Example 2 parts of the ester product as prepared in Example 1, 3.14 parts (0.0142 mol) basic cupric carbonate, and 8.25 parts (0.0569 mol) 8-hydroxyquinoline were heated to 180 C. to obtain a clear concentrate which was soluble on dilution at room temperature in Stoddard solvent, xylol, pine oil, and turpentine.

Example 3 The ester product of 192 parts (1.0 mol) anhydrous citric acid and 388.6 parts (2.0 mols) ethylene glycol p-tert-butylphenyl ether, prepared by heating under a blanket of carbon dioxide, at 165-170 C. until 30 parts of distillate had been collected, dissolved 10% copper- S-quinolinolate when heated to 180 C. The clear concentrate was soluble on dilution in Stoddard solvent, xylol, pine oil and turpentine.

Example 4 The ester product was prepared as in Example 1. 90 parts of the ester, 3.14 parts (0.0142 mol) basic cupric carbonate, and 8.25 parts of (0.0569 mol) 8-hydroxyquinoline were heated to 180 C. The clear concentrate obtained in this manner was soluble on dilution in Stoddard solvent, xylol, pine oil, and turpentine.

Example 5 The mixed ester product of 143.2 parts (1.1 mol) 2 ethyl hexanol, 194.3 parts (1.0 mol) ethylene glycol ptert-butylphenyl ether, and 192.1 parts 1.0 mol) citric acid prepared in situ with sufficient copper-8-quinolinolate to yield a 10% concentrate after removal of water and unreacted 2 ethyl hexanol, was clear and easily soluble on dilution in the cold in Stoddard solvent, xylol, turpentine, pine oil, and perchlorethylene.

Example 7 32.6 parts (0.170 mol) anhydrous citric acid, 33.1 parts (0.170 mol) ethylene glycol p-tert-butylphenyl ether, 24.4 parts (0.187 mol) 2 ethyl hexanol, 3.14 parts (0.0142 mol) basic cupric carbonate, and 8.25 parts (0.0569 mol) 8-hydroxyquinoline were heated at C. for one hour until 35 parts of aqueous distillate had been collected. The clear concentrate was soluble on dilution at room temperature in Stoddard solvent, xylol, pine oil, and turpentine.

Example The ester product of 192.1 parts (1.0 mol) anhydrous citric acid and 416.6 parts (2.0 mols) propylene glycol p-sec-butylphenyl ether, prepared by heating under .a blanket of carbon dioxide at 200 C. to an acid value of 121 and collecting 31 parts of aqueous distillate, dissolved 10% copper-S-quinolinolate when heated to C. The clear concentrate was soluble on dilution in Stoddard solvent, xylol, pine oil and turpentine.

Example 9 The ester product of 192.1 parts (1.0 mol) anhydrous citric acid, 118.2 parts (1.0 mol) ethylene glycol 'butyl ether, and 194.3 parts (1.0 mol) ethylene glycol p-tert '7 hutylphenyl ether, prepared, by heating at 165-175 C. under an atmosphere of nitrogen to collect 31. parts aqueous distillate to an acid value at 167, was found to. dissolve 10% copper-B-quinolinolate when heated to 170 C. The clear concentrate was soluble on dilution in xylol.

Example 10 The ester product of 192.1 parts (1.0 rnol) anhydrous citric acid, and 276.4 parts (2.0 mols) ethylene glycol phenyl ether, prepared by heating at 165-170 C. under an atmosphere of carbon dioxide to collect 30 parts aqueous distillate, was found to dissolve 10% copper-8- quinolinolate when heated to 170 C. The clear concentrate was soluble on dilution in xylol.

Example 11 192.1 parts (1.0 mol) citric acid, 138.2 parts (1.0) ethylene glycol phenyl ether, and 158.3 parts (1.0 mol) n-decanol were heated at 170 C. under an atmosphere of nitrogen for 1 /1 hours to collect 32 parts of aqueous distillate. This ester product was found to dissolve 10% copper-B-quinolinolate. The clear concentrate formed in this manner was soluble on dilution in xylol.

Example 12 192.1 parts (1.0 rnol) anhydrous citric acid, 138.2 parts (1.0 mol) ethylene glycol phenyl ether, 130.2 parts (1.0 rnol) 2 ethyl hexanol were heated at 165-175 C. under an atmosphere of nitrogen to collect 30 parts of aqueous distillate. This ester product was found to dissolve 10% coppcr-8-quinolinola te. The clear concentrated product was soluble on dilution in pine oil, and slightly soluble in xylol.

Example 13 192.1 parts (1.0 mol) anhydrous citric acid, 138.2 parts (1.0 mol) ethylene glycol phenyl ether and 186.4 parts (1.0 mol) trimethyl nonyl alcohol were heated under a blanket of carbon dioxide at 175180 C. to collect 14 parts of aqueous distillate. The ester product dissolved l% copper-8-quinolinolate when heated to 170 C. The clear concentrate was soluble on dilution in xylol and pine oil.

Example 14 The ester product of 192.] parts (1.0 mol) anhydrous citric acid, 300.0 parts (1.0 rnol) polyoxyethylene glycol (molecular weight 300) and 108.1 parts (1.0 mol) benzyl alcohol, prepared by heating at 175480 C. under a blanket of carbon dioxide to collect 37 parts distillate. dissolved copper-8-quinolinolate. The clear concentrate was soluble on dilution in pine oil but insoluble in Stoddard solvent and xylol.

Example 15 304.4 parts (2.0 mols) propylene glycol monophenyl ether and 192.1 parts (1.0 mol) anhydrous citric acid were heated to 170175 C. under an atmosphere of nitrogen to collect 33.5 parts of aqueous distillate. This ester product dissolved 10% copper-8-quinolinolate when heated to 170 C. The clear concentrate was soluble on dilution in xylol.

Example 16.

The ester of 192.1 parts (1.0 mol) anhydrous citric acid, 194.3 parts (1.0 rnol) ethylene glycol p-tert-butylphenyl ether, and 108.1 parts (1.0 mol) benzyl alcohol, prepared by heating at 175-180 C. under an atmosphere of carbon dioxide to obtain parts of aqueous distillate, dissolved 10% copper-8-quinolinolate when heated to 155 C. The. clear concentrate obtained in this manner was soluble on dilution in xylol.

Example 17 192.1 parts 1.0 11101) anhydrous citric acid, 194.3 parts (1.0 mol) ethylene glycol1 p-tert-butylphenyl ether,

and 74.1 parts (1.1 rnol) n-butanol, were heated under a blanket of carbon dioxide to 200 C. to collect 36 parts aqueous distillate. The ester product dissolved 10% copper8-quinolinolate on heating to C. The clear concentrate was soluble on dilution in pine oil, and moderately soluble in xylol.

302 parts (1.0 rnol) of technical methylene di-salicylic acid and 270 parts (1.0 mol) of technical stearyl alcohol were heated at 210-225 C. until 10 parts of water distilled over. The material was diluted with hexane and filtered to remove unreacted acid. After evaporation of the hexane, 5 parts of copper-8-quinolinolate were added to the ester product and heated to 170 C. to form a clear solution. This solution was soluble in Stoddard solvent, xylol, pine oil and butyl acetate.

TYPE H Example 1 42.8 parts (0.319 mol) dipropylene glycol, 47.2 parts (0.319 mol) phthalic anhydride, and 10.0 parts (0.0284 rnol) copper-8-quinolinolate were heated under an atmosphere of carbon dioxide for 30 minutes at 185-190 C. The clear concentrate obtained in this manner was a resinous liquid, soluble on dilution in xylol and pine oil.

Example 2 134.2 parts (1.0 mol) dipropylene glycol, and 148.1 parts (1.0 mol) phthalic anhydride were heated under 1 an atmosphere of carbon dioxide at 185-190 C. for 30 minutes. This ester product dissolved 10% copper-8- quinolinolate when heated to 180 C. The concentrate was soluble on dilution in xylol and pine oil and had identical physical characteristics to the above example.

Example 3 42.8 parts (0.319 mol) dipropylene glycol, 47.2 parts (0.319 mol) phthalic anhydride, 3.14 parts (0.0142 rnol) basic cupric carbonate and 8.25 parts (0.0569 mol) 8- hydroxyquinoline were heated for 30 minutes under an atmosphere of carbon dioxide to 190 C. to obtain a clear concentrate which was soluble on dilution in xylol.

Example 4 134.1 parts (1.0 mol) dipropylene glycol, and 148.1 parts (1.0 mol) phthalic anhydride were heated under an atmosphere of carbon dioxide for 30 minutes at 185- C. 90 parts of this ester product, 3.14 parts (0.0142 rnol) basic cupric carbonate, and 8.25 parts (0.0569 rnol) S-hydroxyquinoline were heated to 180 C. The concentrate was soluble on dilution in xylol.

Example 5 134.2 parts (1 mol) dipropylene glycol and 296.2 parts (2 mols) phthalic anhydride were heated under an atmosphere of carbon dioxide to 210 C. This ester product dissolved 10% copper-S-quinolinolatc when heated to 180 C. The clear concentrate was soluble in dilution in xylol.

Example 6 134.2 parts (1- mol) dipropylene glycol and 296.2 parts (2 mols) phthalic anhydride were heated under an atmosphere of carbon dioxide to 210 C. 90 parts of this ester product, 3.14 parts (0.0142 rnol) basic cupric car- 9 bonate, and 8.25 parts (0.0569 mol) 8-hydroxyquinoline were heatedto 180 C. The clear concentrate obtained in this manner was soluble on dilution in xylol.

Example 7 Example 8 148.1 parts (1.0 mol) phthalic anhydride and 118.9 parts (1.1 mol) benzyl alcohol were heated under an atmosphere of carbon dioxide for 30 minutes at 200 C. This ester product dissolved copper-8-quinolinolate when heated to 190 C. The clear concentrate was so1- uble on dilution in xylol.

Example 9 148.1 parts (1.0 mol) phthalic anhydride, and 118.9 parts (1.1 mols) benzyl alcohol were heated under an atmosphere of carbon dioxide for 30 minutes at 200 C. 90 parts of this ester, 3.14 parts (0.0142 mol) basic cupric carbonate, and 8.25 parts (0.0569 mol) 8-hydroxyquinoline were heated to 190 C. to obtain a clear concentrate which was soluble on dilution in xylol.

Example 10 148.1 parts 1.0 mol) phthalic anhydride and 167.4 parts (1.1 mols) propylene glycol monophenyl ether were heated under an atmosphere of carbon dioxide at 200 C. for 30 minutes. This ester product dissolved 10% copper-8-quinolinolate when heated to 180 C. The exceedingly clear concentrate was soluble on dilution in xylol.

Example 11 148.1 parts (1.0 mol) phthalic anhydride and 167.4

parts (1.1 mols) propylene glycol monophenyl ether were heated under an atmosphere of carbon dioxide at 200 C. for 30 minutes. 90 parts of this ester product, 3.14 parts (0.0142 mol) basic cupric carbonate and 8.25 parts (0.0569 mol) S-hydroxyquinoline were heated to 180 C. The clear concentrate was soluble on dilution in xylol.

Example 12 148.1 parts (1.0 mol) phthalic anhydride, and 213.7 parts (1.1 mols) ethylene glycol p-tert-butylphenyl ether were heated, at 200 C. for 30 minutes. The ester product dissolved 10% copper-S-quinolinolate when heated to 180 C. under a blanket of carbon dioxide. The clear concentrate was a viscous liquid, soluble on dilution in Stoddard solvent and xylol.

Example 13 148.1 parts (1.0 mol) phthalic anhydride, and 213.7 parts (1.1 mols) ethylene glycol p-tert-butylphenyl ether were heated at 200 C. for 30 minutes. 90 parts of this ester product, 3.14 parts (0.0142 mol) basic cupric carbonate and 8.25 parts (0.0569 mol) 8 hydroxyquinoline were heated to 180 C. The clear concentrate was soluble on dilution in Stoddard and xylol.

Example 14 148.1 parts (1.0 mol) phthalic anhydride and 208.3 parts (1.0 mol) propylene glycol p-sec butylphenyl ether were heated at 200 C. for 30 minutes. The ester product dissolved 8% copper-8-quinolinolate when heated to 180 C. The concentrate was soluble on dilution in Stoddard solvent and xylol.

5 dioxide to 175-180 c. for 30 minutes.

'10 Example 15 148.1 parts (1.0 mol) phthalic anhydride and 275.0

parts (1.1 mol) p-octyl phenoxyethanol (Rohm & Haas OPE-1) were heated at 200 C. for 30 minutes. The

ester product dissolved 10% copper-8-quinolinolate when heated to 190 C. The clear concentrate was soluble on dilution in Stoddard solvent and xylol.

Example 16 148.1 parts (1.0 mol) phthalic anhydride and 275.0 parts (1.1 mol) p-octyl phenoxyethanol (Rohm & Haas OPE-1) were heated at 200 C. for 30 minutes. parts of the ester product, 3.14 parts (0.0142 mol) basic cupric carbonate and 8.25 parts (0.569 mol) 8 hydroxyquinoline were heated to 190 C. The clear concentrate obtained in this manner was soluble on dilution in Stoddard solvent and xylol.

Example 17 148.1 parts (1 mol) phthalic anhydride and 138.2 parts (1 mol) ethylene glycol mono phenyl ether were heated to 190 C. for 30 minutes. The ester product dissolved 10% copper-8-quinolinolate when heated to C. The clear concentrate was soluble on dilution in xylol.

Example 18 The ester was prepared as in example 17. 90 parts of the ester, 3.14 parts (0.0142 mol) basic cupric carbonate, and 8.25 parts (0.0569 mol) 8-hydroxyquinoline were heated to 140 C. The clear concentrate obtained was soluble on dilution in xylol.

Example 19 47.9 parts (0.323 mol) phthalic anhydride, 42.1 parts (0.323 mol) 2 ethyl hexanol, and 10.0 parts (0.0284 mol) copper-8-quinolinolate were heated at 175l80 C. for 20 minutes to obtain a clear concentrate which was soluble in xylol.

Example 20 47.9 parts (0.323 mol) phthalic anhydride, 42.1 parts (0.323 mol) 2 ethyl hexanol, 3.14 parts (0.0142 mol) basic cupric carbonate, and 8.25 parts (0.0569 mol) 8- hydroxyquinoline Were heated at 175-l80 C. for 20 minutes to obtain a clear concentrate which was soluble on dilution in xylol.

Example 21 148.1 parts (1.0 mol) phthalic anhydride and 130.2 parts (1.0 mol) 2 ethyl hexanol were heated to C. for 20 minutes under carbon dioxide until an acid value of 214 was reached. The ester product dissolved 10% copper-S-quinolinolate when heated to C. under a carbon dioxide blanket. The clear concentrate was soluble on dilution in xylol.

Example 22 The ester was prepared as in Example 21. 90 parts of the ester, 3.14 parts (0.0142 mol) basic cupric carbonate, and 8.25 parts (0.0569 mol) 8-hydroxyquinoline were heated to 180 C. under carbon dioxide. The clear concentrate was soluble on dilution in xylol.

Example 23 42.5 parts (0.288 mol) phthalic anhydride, 47.5 parts (0.302 mol) n-decanol, and 10.0 parts (0.284 mol) copper-8-quinolinolate were heated under a blanket of carbon dioxide to 175-180" C. for 30 minutes. The clear concentrate was soluble on dilution in xylol, pine oil and turpentine.

Example 24 42.5 parts (0.288 mol) phthalic anhydride, 47.5 parts (0.302 mol) n-decanol, 3.14 parts (0.0142 mol) basic cupric carbonate, and 8.25 parts (0.0569 mol) 8-hydroxyquinoline were heated under an atmosphere of carbon The clear concentrate obtained was soluble. on dilution in xylol. pine oil and turpentine.

Example 25 148.1 parts (1.0 mol) phthalic anhydride, and 165.2 parts (1.5 mols) in n-decanol were heated under a blanket of carbon dioxide at l60-165 C., for 30 minutes. The ester product dissolved coppcr-8-quinolinolate when heated to 180 C. under carbon dioxide. The clear con ccntrate was soluble on dilution in xylol, pine oil and turpentine.

. Example 26 The ester product was prepared as, in Example 24. 90 parts of the ester. 3.14 parts. (0.0142 mol) basic cupric carbonate and 8.25 parts (0.0569 moi) 8-hydroxyquinoline were heated, to 180 C. under carbon dioxide to obtain a clear concentrate soluble in xylol. pine oil and turpentine.

Example 27 296.2 parts (2.0 mols) phthalic auhydridc and 208.] parts (1 .0 mol) tripropylenc glycol were heated to 200 C. under an atmosphere of carbon dioxide. The ester product dissolved 10% copper-tS-quinolinolatc when heated to 180 C. The clear concentrate was soluble on dilution in xylol.

Example 28 The ester was prepared as in Example 27. 90 parts of the ester product. 3.14 parts (0.0142 mol) basic cupric carbonate and 8.25 parts (0.0569 mol) 8'hydroxyquinoline were heated to 180 C. under carbon dioxide to obtain a clear concentrate which Was soluble on dilution in xylol.

Example 29 151.8 parts (1.1 mols) ethylene glycol mono phenyl ether and 196.1 parts (1.0 mol) adipic acid were heated at 210 C. to collect 19 parts of aqueous distillate. 92 parts of the ester product and 8 parts coppcr-8-quinolinolate were heated to 190 C. to obtain a clear concentrate which was soluble on dilution in xylol and pine oil. The product is a solid material at room temperature.

TYPE III Exmnple 1 The ester product of 270 parts (1.0 mol) commercial oleyl alcohol and 192.1 parts (1.0 mol) anhydrous citric acid. prepared by heating at 160-165 C. for 2 hours un der an atmosphere of nitrogen. dissolved 10% copper-3 quinolinolate upon heating further at 160 C. The clear concentrate was soluble on dilution in Stoddard solvent and xylol.

Example 2 The ester was prepared as in Example 1. 3.14 parts (0.0142 mol) basic cupric carbonate, 8.25 parts (0.0569 mol) tl hydroxy-quinoline, and 90 parts of the ester product were heated to 160 C. to obtain a clear concentrate which was soluble on dilution in Stoddard solvent and xylol.

Example 3 284.4 parts (2.0 mols) 3,3,5 trimethyl cyclohexanol and 192.1 parts (1.0 mol) anhydrous citric acid were heatcd under a nitrogen atmosphere at 170180 C. until 32 parts of distillate were collected. This ester product dissolved. 10% copper-S-quiuolinolate when heated to 170 C. The clear concentrate was soluble on dilution in xylol.

Example 4.

The ester product was prepared as in Example 3. 90 parts of the ester, 3.14 parts (0.0142 mol) basic cupric.

carbonate, and 8.25 parts (0.0569 mol) 8-.hydroxyquino-- line were heated to 170 C. to obtain aclear. concentrate whichwas soluble ondilution in xylol.

Example 5 citric acid and 296.4 parts (2.0 mols) dipropylene glycol.

methyl ether, prepared by heating at 175 C. under an atmosphere of nitrogen to collect 31 parts aqueous distillate, solubilized 10% copper-8-quinolino1ate when heated to 205 C. The clear concentrate was soluble on dilution in xylol.

Example 7 56.0 parts (0.354 mol) n-decanol, 34.0 parts (0.177 mol) anhydrous citric acid, and 5.0 parts copper-S-quinolinolate were heated under a blanket of carbon dioxide at 165 C. for one hour. The clear concentrate was soluble on dilution in Stoddard solvent and xylol.

Example 8 The ester product of 316.6 parts (2.0 mols) n-decanol and 192.1 parts (1.0 mol) anhydrous citric acid was prepared by heating at 165 C. to an acid value of 121, under an atmosphere of carbon dioxide. This ester product dissolved 5% copper-B-quinolinolatc when heated to 190 C. The clear concentrate was soluble on dilution in Stoddard solvent and xylol.

Example 9 The ester product of 350 parts (1.0 mol) technical hydroabietyl alcohol, and 150.1 parts (1.0 mol) tartaric acid, prepared by heating at C. for 2 /2 hours to collect 15 parts of aqueous distillate.

TYPE IV Example 1 30.6 parts (0.312 mol) maleic anhydridc, 59.4- parts (0.374 mol) n-decanol, and 10.0 parts (0.0284 mol) copper-S-quinolinolatc were heated under an atmosphere of' carbon dioxide at 165-170 C. for 30 minutes. An inertgas is helpful in preventing oxidation of organic matter and subsequent reduction of copper-3-quinolinolate. The clear concentrate obtained in this manner was soluble in Stoddard solvent and xylol.

Example 2 196.2 parts (2.0 mols) maleic anhydride and 379.9. parts (2.4 mols) n.-dccanol were heatedunder an atmosphere of carbon dioxide at 165-170" C. for 30 minutes. This ester product dissolved. 10% copper-S-quinolinolatc, when heated to 170 C. The concentrate was soluble on dilution in Stoddard solvent and xylol.

Example 3 30.6 parts (0.312 mol) maleic anhydridc, 59.4 parts (0.374 mol) n-decanol, 3.15 parts (0.0142 mol) basic cupric carbonate, and 8.25 parts (0.0569 mol) S-hydroxyquincline were heated under an atmosphere of carbon dioxide at 165170 C. for 30 minutes. The clear. concentrate obtained in this manner was soluble instoddard solvent and xylol.

Example 4 196.2 parts (2.0 mols) maleic anhydride and 379.9 parts (2.4 mols) n-decanol were heated under an atmosphere of carbon dioxide at 165--170 C. for 30 minutes. 90 parts of this ester product, 3.14 parts (0.0.142 mol) basic cupric carbonate, and 8.25 parts-(0056911101) 8-hydroxy- 13 quinoline were heated to 170 C. to obtain a clear concentrate which was soluble on dilution in Stoddard solvent and xylol.

TEST-TENSILE STRENGTH In order to test the fungicidal eifectiveness of this type of solubilized preparation, 2 samples of 80 x 80, 3 ounce cotton percale, 36 inches x 18 inches in area, were treated in Stoddard solvent with the product of Example 5, Type I, so that approximately 10% of the product, equivalent to about 1% copper-8-quinolinolate was deposited on the fabric.

The cloth was then leached in accordance with paragraph 4.3.5 of the QMC specification MIL-D-10860. The procedure consists of the following:

The specimens were thoroughly wetted by immersion with gentle agitation in water at a temperature of 190200 F. for 30 seconds, then immersed for 72 hours in a vessel containing 5.0 gallons of water at 651-5 F. and a pH of 6.0 to 8.0. The vessel was emptied and refilled every hours so that there were 6 changes of water during the 72 hour period. The samples were removed at the end of 72 hours, dried, and conditioned before submitting to the soil burial test. 7

The samples were buried in accordance with section VIII, paragraph 4, of the supplement to Federal specification CCC-T-191, except that the samples were not sterilized. The specimens were removed from the soil, rinsed to remove any adhering soil, dried at 212 F., and conditioned for breaking strength tests.

The results of the tensile strength tests are given in the following table:

The numerous examples above which represent concentrated solution preparations, which have been made, are ofiered to show the range of materials investigated and other factors. But the methods of preparation of each of the compositions may be varied. And the metallic derivatives of cobalt, lead, iron, aluminum, magnesium, manganese and tin can be formed by methods analogous to some of those set out in detail. And to include them all would needlessly lengthen the disclosure. The copper derivative is quite fungicidal, the zinc derivative is weakly so and the nickel derivative is not fungicidal.

Examples on the last two types, less important in this respect, are herewith given:

EXAMPLES ON SOLUBILIZING ZINC- AND NICKEL-8-QUINOLINOLATES Example 1 Example 2 712 parts (0.029 mol) nickel acetate, 8.4 parts (0.0337 mol) 8-hydroxyquinoline and 90 parts of the ester product of 192 parts (1.0 mol) anhydrous citric acid, 143 parts (1.1 mols) 2 ethyl hexanol, and 229 parts (1.1 mols) propylene glycol-o-sec-butylphenyl ether, were heated to 190 C. to obtain a clear concentrate, which was soluble on dilution in Stoddard solvent and xylol.

We have observed that for optimum solubilization, the polar, acid ester of diand tri-carboxylic acids (true for mixed esters too) should be a relatively non-crystallizing or resinous or viscous material. The partial ester product of 1.0 mol of citric acid and 2.0 mols of trimethyl cyclohexanol is a resinous liquid which sets to a glass; it retains the copper-8-quinolinolate in solution at low temperatures. This contrasts with the partial ester product of 1.0 mol'of phthalic anhydride and 1.0 mol of trimethyl cyclohexanol. The latter is a very strongly crystalline solid; it' dissolves copper-8-quinolinolate at temperatures as low as l20-140 C. but on cooling most of this solute also crystallizes out.

There is no need to present at length the uses of the solutions formed upon dilution of the concentrated solution formed by solubilizing the insoluble copper-8- quinolinolate. For the two U. S. patents referred to previously 2,561,379 and 2,561,380 amply describe uses of dilute solution of this compound.

It is believed that when the copper-8-quinolinolate or other derivatives thereof are treated with the polar, acid esters of polycarboxylic acids in the manner herein described that there is formed a true solution. Perhaps it is colloidal. We have observed that the solutions are clear. Those of copper derivative are clear, bright greenish-black.

Many of these copper-8-quinolinolate solutions can be easily dispersed in water with the aid of emulsifying agent so that the copper-8-quinolinolate is well dispersed for aqueous applications. 8 I

Metallic soaps, including nickel, cobalt, copper, lead, zinc, iron, aluminum, manganese, magnesium, zirconium and tin soaps of the common fatty acids and napthenic acids, may be incorporated with these copper-S-quinolinolate concentrated solutions in order to obtain water repellency or other characteristics. The metallic quinolinolate having already been put in solution by the polar, acid esters of diand tri-carboxylic acids by ways we have taught, the metallic soaps have a difierent role or function to perform when added. These types of soaps tend to promote the formation of water-in-oil emulsions which can be a form having desirability in applying fungicides. Certain of these soaps are known to possess atmospheric drying properties which could be utilized in applying the fungicide.

Although numerous examples have been given herein all of which have been actually made in the laboratory, other variations can be made in forming the concentrated solutions. Hence we do not intend to be limited except by the scope of the appended claims taken in conjunction with the entire disclosure.

We claim as our invention: 7

1. The method of solubilizing a polyvalent metallic-8- quinolinolate whose metallic radical is from the group consisting of copper, nickel and zinc, consisting of heating it with an acid ester of an organic polycarboxylic acid, the equivalent weight of which ester comes within the range of to 750, the polycarboxylic acid radical being a member of the group consisting of paraflin di-carboxylic acids, hydroxy-paraffin di-carboxylic acids, olefine dicarboxylic acids, parafiin tri-carboxylic acids, hydroxyparaffin tri-carboxylic acids, olefine tri-carboxylic acids and phenyl di-carboxylic acids, the alcohol radical being a member of the group consisting of the aliphatic hydrocarbon alcohols and their phenyl ether substituted derivative, lower alkylene glycol ethers, alkyl substituted cyclohexanol, phenyl alkylols, hydroabietyl alcohol, phenoxy alkylols, and hydrocarbon substituted alkylols, under thoroughagitation until a concentrated solution is formed, which is soluble upon dilution in a volatile liquid organic solvent including at least one member of the group consisting of. Stoddard solvent, mineral spirits,

pine oil, xylol, turpentine, carbon tetrachloride and ethyl acetate.

2. The method of solubilizing a polyvalent metallic- S-quinolinolate whose metallic radical is from the group consisting of copper, nickel and zinc, consisting of heating it with an acid ester of an organic polycarboxylic acid, the equivalent weight of which ester comes within the range of 350 to 500, the polycarboxylic acid radical being a member of the group consisting of paraffin di-carboxylic acids, hydroxy-paratfin di-carboxylic acids, olefine dicarboxylic acids, paratfin tri-carboxylic acids, hydroxyparattin tri-carboxylic acids, olefine tri-carboxylic acids and phenyl di-carboxylic acids, the alcohol radical being a member of the group consisting of the aliphatic hydrocarbon alcohols and their phenyl ether substituted derivative, lower alkylene glycol ethers, alkyl substituted cyclohexanol, phenyl alkylols, hydroabietyl alcohol, phenoxy alkylols, and hydrocarbon substituted alkylols, under thorough agitation until a concentrated solution is formed, which is soluble upon dilution in a volatile liquid organic solvent including at least one member of the group consisting of Stoddard solvent, mineral spirits, pine oil, xylol, turpentine, carbon tetrachloride and ethyl acetate.

3. The method of solubilizing copper-8-quinolinolate consisting of heating it with an acid ester of an organic polycarboxylic acid, the equivalent weight of which ester comes within the range of 100 to 750, the polycarboxylic acid radical being a member of the group consisting of paraffin di-carboxylic acids, hydroxyparaffin di-carboxylic acids, olefine di-carboxylic acids, parafiin tri-carboxylic acids, hydroxy-paraflin tri-carboxylic acids, olefine tricarboxylic acids and phenyl dicarboxylic acids, the alcohol radical being a member of the group consisting of the aliphatic hydrocarbon alcohols and their phenyl ether substituted derivative, lower alkylene glycol ethers, alkyl substituted cyclohexanol, phenyl alkylols, hydroabietyl alcohol, phenoxy alkylols, and hydrocarbon substituted alkylols, under thorough agitation until a concentrated solution is formed, which is soluble upon dilution in a volatile liquid organic solvent including at least one member of the group consisting of Stoddard solvent, mineral spirits, pine oil, xylol, turpentine, carbon tetrachloride and ethyl acetate.

4. The method of solubilizing copper-8-quinolinolate consisting of heating it with an acid ester of an organic polycarboxylic acid, the equivalent Weight of which ester comes within the range of 350 to 500, the polycarboxylic acid radical being a member of the group consisting of parattin di-carboxylic acids, hydroxy-paraffin di-carboxylic acids, olefine di-carboxylic acids, paraffin tri-carboxylic acids, hydroxy-parafiin tri-carboxylic acids, olefine tricarboxylic acids and phenyl di-carboxylic acids, the alcohol radical being a member of the group consisting of the aliphatic hydrocarbon alcohols and their phenyl ether substituted derivative, lower alkylene glycol ethers, alkyl substituted cyclohexanol,. phenyl alkylols, hydroabietyl alcohol, phenoxy alkylols, and hydrocarbon substituted alkylols, under thorough agitation until a concentrated. solution is formed, which is soluble upon dilution in a volatile liquid organic solvent including at least one member of the group consisting of Stoddard solvent, mineral spirits, pine oil, xylol, turpentine, carbon tetrachloride and ethyl acetate.

5. A concentrated solution of. a water-insoluble metallic salt of S-hydroxyquinolinolate.whosemetallic radical is a member of the group consisting of copper, nickel and zinc, in an acid ester of an organic polycarboxylic acid, the equivalent weight of which ester comes within the range 100 to750, the polycarboxylic acid radical being a member of the groupconsisting of paraflin di-carboxylic acids, hydroxy-parafii'n di-carboxylic. acids, olefine dicarboxylic acids, parafiin tri-carb'oxylic acids, hydroxyparatlin tri-carboxylic acids, olefine tri-carboxylic acids and phenyl di-carboxylic acids, the alcohol radical being a member of the group consisting of the aliphatic hydrocarbon alcohols and their phenyl ether substituted derivative, lower alkylene glycol ethers, alkyl substituted cyclohexanol, phenyl alkylols, hydroabietyl alcohol, phenoxy alkylols, and hydrocarbon substituted alkylols, which concentrated solution is soluble upon dilution in a volatile organic liquid including at least one member of the group consisting of Stoddard solvent, mineral spirits, pine oil, xylol, turpentine, carbon tetrachloride and ethyl acetate.

6. A concentrated solution of a water-insoluble metallic salt of 8-hydrox'yquinolinolate whose metallic radical is a member of the group consisting of copper, nickel and zinc, in an acid ester of an organic polycarboxylic acid, the equivalent weight of which ester comes within the range of 350 to 500, the polycarboxylic acid radical being a member of the group consisting of parafl'in di-carboxylic acids, hydroxy-parafiin di-carboxylic acids, olefine dicarboxylic acids, parafiin tri-carboxylic acids, hydroxyparaffin tri-carboxylic acids, olefine tri-carboxylic acids and phenyl di-carboxylic acids, the alcohol radical being a member of the group consisting of the aliphatic hydrocarbon alcohols and their phenyl ether substituted derivative, lower alkylene glycol ethers, alkyl substituted cyclohexanol, phenyl alkylols, hydroabietyl alcohol, phenoxy alkylols, and hydrocarbon substituted alkylols, which concentrated solution is soluble upon dilution in a volatile organic liquid including at least one member of the group consisting of Stoddard solvent, mineral spirits, pine oil, Xylol, turpentine, carbon tetrachloride and ethyl acetate.

7. A concentrated solution of copper-8-quinolinolate in an acid ester of an organic polycarboxylic acid, the equivalent Weight of which ester comes within the range to 750, the polycarboxylic acid radical being a member of the group consisting of paraffin di-carboxylic acids, hydroxy-parafiin di-carboxylic acids, olefine di-carboxylic acids, paraffin tri-carboxylic acids, hydroXy-paratfin tricarboxylic acids, olefine tri-carboxylic acids and phenyl di-carboxylic acids, the alcohol radical being a member of the group consisting of the aliphatic hydrocarbon alcohols and their phenyl ether substituted derivative, lower alkylene glycol ethers, alkyl substituted cyclohexanol, phenyl alkylols, hydroabietyl alcohol, phenoxy alkylols, and hydrocarbon substituted alkylols, which concentrated solution is soluble upon dilution in a volatile organic liquid including at least one member of the group consisting of Stoddard solvent, mineral spirits, pine oil, xylol, turpentine, carbon tetrachloride and ethyl acetate.

8. A- con'centrated solution of copper-8-quinolinolate in an acid ester of an organic polycarboxylic acid, the equivalent weight of which ester comes within the range of 350 to 500, the polycarboxylic acid radical being a member of the group consisting of parafiin di-carboxylic acids, hydroxy-paraffin di-carboxylic acide, olefine dicarboxylic acids, paraffin tri-carboxylic acids, hydroxyparafiin tri-carboxylic acids, olefine tri-carboxylic acids and phenyl di-carboxylic acids, the alcohol radical being a member of the group consisting of the aliphatic hydrocarbon alcohols and their phenyl ether substituted derivative, lower alkylene glycol ethers, alkyl substituted cyclohexanol, phenyl alkylols, hydroabietyl alcohol, phenoxy alkylols, and hydrocarbon substituted alkylols, which concentrated solution is soluble upon dilution in a volatile organic liquid including at least one member of the group consisting of Stoddard solvent, mineral spirits, pine oil, xylol, turpentine, carbon tetrachloride and ethyl acetate.

9. A concentrated solution of a water-insoluble metallic-8-quinolinolate, whose metallic radical is a member of the group consisting of copper, nickel and zinc, in an acid ester of a polycarboxylic acid, the equivalent Weight of which esters comes within the range of 100 to 750, the ester being of a hydroxy-paratfin di-carboxylic 17 acid and benzyl alcohol, the concentrated solution being soluble upon dilution in a volatile organic liquid including at least one member of the group consisting of Stoddard solvent, mineral spirits, pine oil, Xylol, turpentine, carbon tetrachloride and ethyl acetate.

10. A concentrated solution of a water-insoluble rnetallic-8-quinolinolate, whose metallic radical is a member of the group consisting of copper, nickel and zinc, in an acid ester of a polycarboxylic acid, the equivalent weight of which ester comes within the range of 100 to 750, the ester being of a hydroxy-paralfin tri-carboxylic acid and benzyl alcohol, the concentrated solution being soluble upon dilution in a volatile organic liquid including at least one member of the group consisting of Stoddard solvent, mineral spirits, pine oil, xylol, turpentine, carbon tetrachloride and ethyl acetate.

11. A concentrated solution of a water-insoluble metallic-S-quinolinolate whose metallic radical is a member of the group consisting of copper, nickel and zinc, in an acid ester of a polycarboxylic acid, the equivalent weight of which ester comes within the range 100 to 750, the ester being of citric acid and phenyl alcohol, the said ester being soluble upon dilution in a volatile liquid organic solvent including at least one member of the group consisting of Stoddard solvent, mineral spirits, pine oil, Xylol, turpentine, carbon tetrachloride and ethyl acetate.

12. A concentrated solution of a water-insoluble metallic-8-quinolinolate whose metallic radical is a member of the group consisting of copper, nickel and zinc, in an acid ester of a polycarboxylic acid, the equivalent weight of which ester comes within the range 100 to 750, the ester being of citric acid and ethylene glycol sec. butylphenyl ether, the said ester being soluble upon dilution in a volatile liquid organic solvent including at least one member of the group consisting of Stoddard solvent, mineral spirits, pine oil, xylol, turpentine, carbon tetrachloride and ethyl acetate.

13. A concentrated solution of a water-insoluble metallic-8-quinolinolate Whose metallic radical is a member of the group consisting of copper, nickel and zinc, in an acid ester of a polycarboxylic acid, the equivalent Weight of which ester comes within the range to 750, the ester being of phthalic acid and dipropylene glycol, the said ester being soluble upon dilution in a volatile liquid organic solvent including at least one member of the group consisting of Stoddard solvent, mineral spirits, pine oil, xylol, turpentine, carbon tetrachloride and ethyl acetate.

14. A concentrated solution of a water-insoluble metallic-S-quinolinolate whose metallic radical is a member of the group consisting of copper, nickel and Zinc, in an acid ester of a polycarboxylic acid, the equivalent weight of which ester comes within the range 100 to 750, the ester being of citric acid and an aliphatic hydrocarbon alcohol, the said ester being soluble upon dilution in a volatile liquid organic solvent including at least one member of the group consisting of Stoddard solvent, mineral spirits, pine oil, xylol, turpentine, carbon tetrachloride and ethyl acetate.

References Cited in the file of this patent UNITED STATES PATENTS 2,561,379 Kalberg July 24, 1951 2,561,380 Kalberg July 24-, 1951 2,561,553, Ashford July 24, 1951 

1. THE METHOD OF SOLUBILIZING A POLYVALENT METALLIC-8QUINOLINOLATE WHOSE METALLIC RADICAL IS FROM THE GROUP CONSISTING OF COPPER, NICKEL AND ZINC, CONSISTING OF HEATING IT WITH AN ACID ESTER OF AN ORGANIC POLYCARBOXYLIC ACID, THE EQUIVALENT WEIGHT OF WHICH ESTER COMES WITHIN THE RANGE OF 100 TO 750, THE POLYCARBOXYLIC ACID RADICAL BEING A MEMBER OF THE GROUP CONSISTING OF PARAFFIN DI-CARBOXYLIC ACIDS, HYDROXY-PARAFFIN DI-CARBOXYLIC ACIDS, OLEFINE DICARBOXYLIC ACIDS, PARAFFIN TRI-CARBOXYLIC ACIDS, HYDROXYPARAFFIN TRI-CARBOXYLIC ACIDS, OLEFINE TRI-CARBOXYLIC ACIDS AND PHENYL DI-CARBOXYLIC ACIDS, THE ALCOHOL RADICAL BEING A MEMBER OF THE GROUP CONSISTING OF THE ALIPHATIC HYDROCARBON ALCOHOLS AND THEIR PHENYL ETHER SUBSTITUTED DERIVATIVE, LOWER ALKYLENE GLYCOL ETHERS, ALKYL SUBSTITUTED CYCLOHEXANOL, PHENYL ALKYLOLS, HYDROABIETYL ALCOHOL, PHENOXY ALKYLOLS, AND HYDROCARBON SUBSTITUTED ALKYLOLS, UNDER THOROUGH AGITATION UNTIL A CONCENTRATED SOLUTION IS FORMED, WHICH IS SOLUBLE UPON DILUTION IN A VOLATILE LIQUID ORGANIC SOLVENT INCLUDING AT LEAST ONE MEMBER OF THE GROUP CONSISTING OF STODDARD SOLVENT, MINERAL SPIRITS, PINE OIL, XYLOL, TURPENTINE, CARBON TETRACHLORIDE AND ETHYL ACETATE. 